Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/52—Amides or imides
  • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
  • C08F20/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-acryloylmorpholine
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F6/00—Post-polymerisation treatments
  • C08F6/06—Treatment of polymer solutions
  • C08F6/12—Separation of polymers from solutions

Definitions

• the present invention relates to a method for producing concentrates containing polymers based on acryloyldimethyltauric acid or its salts, obtainable by polymerizing acryloyldimethyltauric acid and / or Acryloyldimethyltaurates in the presence of one or more olefinic Comonomers, polymeric additives and components with functional groups.
• WO 02/44231 describes a new class of polymers based on Acryloyldimethyltauric acid or its salts are described. These polymers cover broad application properties and can be used as thickeners, Consistency agent, emulsifier, dispersant, lubricant, conditioner and / or Stabilizer in cosmetic, dermatological and pharmaceutical agents be used.
• copolymers preferably produced by precipitation polymerization based on Acryloyldimethyltauric acid or its salts according to the state of the Technology are powdery substances with resulting application disadvantages.
• powdery substances contain Risk of dust explosion, furthermore the storage stability of the powder due to hygroscopy impaired.
• the Dissolving process For processing or using the powdery products is the Dissolving process (the polymers are preferably incorporated into aqueous media) mostly very time consuming.
• the dissolving process of the powdery products can, depending depending on the size of the batch, one hour and more.
• special stirring and Dispersing devices required to make the polymers To dissolve acryloyldimethyltauric acid or its salts in the agents, or to suspend.
• the object of the present invention was to develop a one-pot process for Production of polymer concentrates containing polymers based on Acryloyldimethyltauric acid or its salts in highly concentrated liquid or liquid-dispersed form with the highest possible polymer content and low viscosity with high stability of the solution or dispersion in a cosmetic and pharmaceutically acceptable matrix.
• Another object of the invention are the concentrates, which according to the Processes according to the invention have been produced.
• the Acryloyldimethyltauraten can be the inorganic or organic salts of Acryloyldimethyltaurinklare (Acrylamidopropyl-2-methyl-2-sulfonic acid).
• the Li + , Na + , K + , Mg ++ , Ca ++ , Al +++ and / or NH 4 + salts are preferred.
• the monoalkylammonium, dialkylammonium, trialkylammonium and / or tetraalkylammonium salts are likewise preferred, it being possible for the alkyl substituents of the amines, independently of one another, to be (C 1 -C 22 ) alkyl radicals or (C 2 -C 10 ) hydroxyalkyl radicals. Furthermore, mono- to triple-ethoxylated ammonium compounds with different degrees of ethoxylation are also preferred. Mixtures of two or more of the above representatives are also within the meaning of the invention.
• the degree of neutralization of acryloyldimethyltauric acid can be between 0 and 100%, a degree of neutralization of above 80% is particularly preferred.
• the content of acryloyldimethyltauric acid is or acryloyldimethyl taurates at least 0.1% by weight, preferably 20 to 99.5% by weight and particularly preferably 50 to 98% by weight.
• silicone-containing substances of component D) at least mono olefinically unsaturated compounds suitable among the enabled reaction conditions chosen for radical polymerization are.
• the distribution of the individual silicone-containing monomers over the resulting polymer chains do not necessarily take place statistically.
• the formation of, for example, block (also multiblock) or gradient-like structures is in the sense of the invention. Combinations of two or several different silicone-containing representatives are also possible.
• the Use of silicone-containing substances with two or more polymerization-active groups lead to the formation of branched or cross-linked Structures.
• Preferred silicone-containing substances are those of the formula (I) R 1 - Z- [(Si (R 3 R 4 ) -O-) w - (Si (R 5 R 6 ) -O) x -Si (R 8 R 9 )) - R 2
• R 1 represents a polymerizable radical from the group of vinylically unsaturated compounds, which is suitable for building polymeric structures by radical means.
• a suitable chemical bridge Z is required to connect the silicone-containing polymer chain to the reactive end group R 1 .
• Preferred bridges Z are -O-, -O - ((C 1 -C 50 ) alkylene) -, - O - ((C 6 -C 30 ) arylene) -, - O - ((C 5 -C 8 ) cycloalkylene ) -, -O - ((C 1 -C 50 ) alkenylene) -, - (polypropylene oxide) n -, - (polyethylene oxide) o -, - (polypropylene oxide) n (polyethylene oxide) o -, where n and o are independent numbers mean from 0 to 200 and the distribution of the EO / PO units can be statistical or block-shaped.
• Z bridge groupings -O - ((C 1 - C 10 ) alkylene) - (Si (OCH 3 ) 2 ) -O- and -O- (Si (OCH 3 ) 2 ) -O-.
• the polymer middle section is made up of silicone-containing repeat units represents.
• the radicals R 3 , R 4 , R 5 and R 6 independently of one another are -CH 3 , -O-CH 3 , -C 6 H 5 or -OC 6 H 5 .
• the radicals R 8 and R 9 independently of one another are -CH 3 , -O-CH 3 , -C 6 H 5 , -OC 6 H 5 or -O-Si (CH 3 ) 3 .
• the indices w and x represent stoichiometric coefficients that are independent from each other 0 to 500, preferably 10 to 250.
• the distribution of the repeating units across the chain cannot only be pure statistical, but also block-like, alternating or gradient-like.
• R 2 can symbolize on the one hand an aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (C 1 -C 50 ) hydrocarbon radical (linear or branched) or mean -OH, -NH 2 , -N (CH 3 ) 2 or -R 7 or represent the structural unit [-ZR 1 ], where Z and R 1 have the meaning given above.
• R 7 stands for further Si-containing groups.
• R 7 radicals are -O-Si (CH 3 ) 3 , -O-Si (Ph) 3 , -O-Si (O-Si (CH 3 ) 3 ) 2 CH 3 ) and -O-Si (O -Si (Ph) 3 ) 2 Ph).
• R 2 represents an element of the group [-ZR 1 ], it is a matter of difunctional monomers which can be used to crosslink the resulting polymer structures.
• Formula (I) describes not only vinylically functionalized, silicone-containing Polymer species with a typical polymer distribution, but also defined Discrete molecular weight compounds.
• Particularly preferred silicone-containing substances are the following acrylic- or methacrylic-modified silicone-containing substances:
• the content of silicon-containing Components up to 99.9% by weight, preferably 0.5 to 30% by weight, in particular preferably 1 to 20% by weight.
• Preferred fluorine-containing substances of component E) are those according to formula (II).
• R 1 represents a polymerizable function from the group of vinylically unsaturated compounds, which is suitable for building polymer structures by radical means.
• a suitable chemical bridge Y is required to connect the fluorine-containing group to the reactive end group R 1 .
• Preferred bridges Y are -O-, -C (O) -, - C (O) -O-, -S-, -O-CH 2 -CH (O -) - CH 2 OH, -O-CH 2 - CH (OH) -CH 2 -O-, -O-SO 2 -O-, -OS (O) -O-, -PH-, -P (CH 3 ) -, -PO 3 - -NH-, - N (CH 3 ) -, -O- (C 1 -C 50 ) alkyl-O-, -O-phenyl-O-, -O-benzyl-O-, -O- (C 5 -C 8 ) cycloalkyl- O-, -O- (C 1 -C 50 ) alkenyl-O-,
• R and s are stoichiometric coefficients that are independent from each other, numbers from 0 to 200 mean.
• Preferred fluorine-containing substances of component E) according to formula (II) are Perfluorohexylethanol methacrylate, Perfluorhexoylpropanol methacrylate, Perfluoroctyethanol methacrylate, Perfluoroctylpropanol methacrylate, Perfluorhexylethanolylpolygycolether methacrylate, Perfluorhexoyl-propanolyl-poly [ethylene glycol-co-propylene glycol] acrylate, Perfluoroctyethanolyl-poly [ethylene glycol-block co-propylene glycol] methacrylate, Perfluoroctylpropanolyl-polypropylene-glycol ether methacrylate.
• the content of fluorine-containing Components up to 99.9% by weight, preferably 0.5 to 30% by weight, in particular preferably 1 to 20% by weight.
• the macromonomers of component F) are at least simple olefinically functionalized polymers with one or more discrete Repeat units and a number average molecular weight greater or greater equal to 200 g / mol. Mixtures can also be chemically mixed in the polymerization different macromonomers of component F) are used. Both Macromonomers are polymer structures that consist of one or several repetition unit (s) are constructed and one for polymers have characteristic molecular weight distribution.
• R 1 represents a polymerizable function from the group of the vinylically unsaturated compounds which are suitable for building polymer structures by radical means.
• a suitable bridging group Y is required to connect the polymer chain to the reactive end group.
• Preferred bridges Y are -O-, -C (O) -, - C (O) -O-, -S-, -O-CH 2 -CH (O -) - CH 2 OH, -O-CH 2 - CH (OH) -CH 2 O-, -O-SO 2 -O-, -O-SO 2 -O-, -O-SO-O-, -PH-, -P (CH 3 ) -, -PO 3 -, -NH- and -N (CH 3 ) -, particularly preferably -O-.
• the polymeric middle part of the macromonomer is characterized by the discrete Repeat units A, B, C and D represent.
• preferred Repeating units A, B, C and D are derived from acrylamide, methacrylamide, Ethylene oxide, propylene oxide, acryloyldimethyltauric acid, acrylic acid, methacrylic acid, Methyl methacrylate, acrylonitrile, maleic acid, vinyl acetate, styrene, 1,3-butadiene, Isoprene, isobutene, diethylacrylamide and diisopropylacrylamide.
• indices v, w, x and z in formula (III) represent the stoichiometric Coefficients related to the repeating units A, B, C and D.
• v, w, x, and z are independently 0 to 500, preferably 1 to 30, the sum of the four coefficients must be ⁇ 1 on average.
• the distribution of the repeating units over the macromonomer chain can be statistical, block-like, alternating or gradient-like.
• R 2 represents a linear or branched aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (C 1 -C 50 ) hydrocarbon radical, OH, -NH 2 , -N (CH 3 ) 2 or is identical to the structural unit [-YR 1 ].
• R 2 equal to [-YR 1 ]
• these are difunctional macromonomers which are suitable for crosslinking the copolymers.
• Particularly preferred macromonomers of component F) are acrylic or methacrylic monofunctionalized alkyl ethoxylates of the formula (IV).
• R 3 , R 4 , R 5 and R 6 are independently hydrogen or n-aliphatic, iso-aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (C 1 -C 30 ) hydrocarbon radicals.
• R 3 and R 4 are preferably H or -CH 3 , particularly preferably H.
• R 5 is preferably H or -CH 3 .
• R 6 is preferably an n-aliphatic, iso-aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (C 1 -C 30 ) hydrocarbon radical.
• R 6 is preferably an alkyl radical having 8 to 24 carbon atoms, particularly preferably having 12 to 22 carbon atoms.
• v and w are again the stoichiometric coefficients regarding the Ethylene oxide units (EO) and propylene oxide units (PO).
• EO Ethylene oxide units
• PO propylene oxide units
• v and w independently of one another 0 to 500, preferably 1 to 30, the sum of v and w must be ⁇ 1 on average.
• the distribution of the EO and PO units over the Macromonomer chains can be statistical, block-like, alternating or gradient-like his.
• FIG. 1 Further particularly preferred macromonomers of component F) have the following structure according to formula (IV): description R 3 R 4 R 5 R 6 v w Genapol® LA-030 methacrylate H H -CH 3rd lauryl 3 0 Genapol® LA-070 methacrylate H H -CH 3rd lauryl 7 0 Genapol ® LA-200 methacrylate H H -CH 3rd lauryl 20 0 Genapol ® LA-250 methacrylate H H -CH 3rd lauryl 25 0 Genapol ® T-080 methacrylate H H -CH 3rd TALK 8th 0 Genapol® T-080 acrylate H H H TALK 8th 0 Genapol ® T-250 methacrylate H H -CH 3rd TALK 25 0 Genapol ®T-250 crotonate -CH 3rd H -CH 3rd TALK 25 0 Genapol ®
• Genapol® types are products from Clariant GmbH.
• the molecular weight of the macromonomers of component F) is preferably 200 g / mol to 10 6 g / mol, particularly preferably 150 to 10 4 g / mol and particularly preferably 200 to 5000 g / mol.
• Suitable macromonomers based on the total mass of the polymers up to 99.9% by weight can be used.
• the ranges are preferably 0.5 to 30% by weight and 70 to 99.5% by weight application. Portions are particularly preferred from 1 to 20% by weight and 75 to 95% by weight.
• the polymerization is in the presence carried out at least one polymeric additive of component G), which Additive of component G) before the actual polymerization Polymerization medium is added completely or partially dissolved.
• the Use of several additives of component G) is also possible according to the invention.
• Crosslinked additives of component G) can also be used.
• the additives of component G) or their mixtures only have to be whole or be partially soluble in the chosen polymerization medium.
• the additive of component G) has several Functions. On the one hand, it prevents the in the actual polymerization step Formation of crosslinked polymer parts in the polymer that forms and on the other hand, the additive of component G) according to the generally known Mechanism of graft copolymerization of active radicals statistically attacked. This means that depending on the additive of component G) more or less large parts of it are incorporated into the polymers. Also own suitable additives of component G) the property, the solution parameters of the forming polymers during the radical polymerization reaction in such a way to change that the average molecular weights shifted to higher values become. Compared to analog polymers that do not contain additives Component G) were produced, show those with the addition of additives component G) were produced, advantageously a significantly higher one Viscosity in aqueous solution.
• Preferred as additives of component G) are in water and / or alcohols, preferably homopolymers and copolymers soluble in t-butanol. Among copolymers are to understand those with more than two different types of monomers.
• Homo- and copolymers are particularly preferred as additives of component G) from N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, ethylene oxide, propylene oxide, Acryloyldimethyltauric acid, N-vinylcaprolactam, N-vinylmethyl-acetamide, Acrylamide, acrylic acid, methacrylic acid, N-vinylmorpholide, hydroxyethyl methacrylate, Diallyldimethylammonium chloride (DADMAC) and / or [2- (methacryloyloxy) ethyl] trimethylammonium chloride (MAPTAC); Polyalkylene glycols and / or alkyl polyglycols.
• Polyvinylpyrrolidones are particularly preferred as additives of component G) (e.g. Luviskol K15®, K20® and K30® from BASF), poly (N-vinylformamide), poly (N-vinylcaprolactame) and copolymers of N-vinyl pyrrolidone, N-vinyl formamide and / or acrylic acid, which can also be partially or completely saponified.
• component G e.g. Luviskol K15®, K20® and K30® from BASF
• poly (N-vinylformamide) poly (N-vinylcaprolactame)
• copolymers of N-vinyl pyrrolidone, N-vinyl formamide and / or acrylic acid which can also be partially or completely saponified.
• the molecular weight of the additives of component G) is preferably 10 2 to 10 7 g / mol, particularly preferably 0.5 * 10 4 to 10 6 g / mol.
• the amount of polymeric additive used for component G) is based on the total mass of the monomers to be polymerized during the polymerization, preferably 0.1 to 90% by weight, particularly preferably 1 to 20% by weight and particularly preferably 1.5 to 10% by weight.
• radical polymerization For the other substances that in addition to acryloyldimethyltauric acid and / or Acryloyldimethyltaurates and the substances selected from one or more components D) to G) are present during the radical polymerization, it is preferably further at least monofunctional, for radical polymerization capable comonomers or polymeric additives.
• substances Component BC are selected below as substances Component BC.
• the comonomers are the Component B) from olefinically unsaturated, non-cationic, if appropriate crosslinking comonomers containing at least one oxygen, nitrogen, sulfur or Have a phosphorus atom and a molecular weight of less than 500 g / mol, selected.
• Unsaturated carboxylic acids are preferred as comonomers of component B) and their anhydrides and salts, and their esters with aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic alcohols with a Carbon number from 1 to 30.
• Particularly preferred unsaturated carboxylic acids are acrylic acid, Methacrylic acid, styrene sulfonic acid, maleic acid, fumaric acid, crotonic acid, Itaconic acid and senecioic acid.
• Preferred counterions are Li + , Na + , K + , Mg ++ , Ca ++ , Al +++ , NH 4 + , monoalkylammonium, dialkylammonium, trialkylammonium and / or tetraalkylammonium radicals, where the alkyl substituents are Amines can independently of one another be (C 1 -C 22 ) alkyl radicals or (C 2 -C 10 ) hydroxyalkyl radicals.
• mono- to triple-ethoxylated ammonium compounds can also be used different degrees of ethoxylation find application.
• the degree of neutralization the carboxylic acids can be between 0 and 100%.
• Open-chain comonomers of component B) are also preferred N-vinylamides, preferably N-vinylformamide (VIFA), N-vinylmethylformamide, N-vinyl methylacetamide (VIMA) and N-vinylacetamide; cyclic N-vinyl amides (N-vinyl lactams) with a ring size of 3 to 9, preferably N-vinyl pyrrolidone (NVP) and N-vinylcaprolactam; Amides of acrylic and methacrylic acid, preferably acrylamide, Methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide and N, N-diisopropylacrylamide; alkoxylated acrylic and methacrylamides, preferred Hydroxyethyl methacrylate, hydroxymethyl methacrylamide, Hydroxyethyl methacrylamide, hydroxypropyl methacrylamide and succinic acid mono- [2- (methacryloyl
• Inorganic acids are also suitable as comonomers of component B) and their salts and esters.
• Preferred acids are vinylphosphonic acid, Vinylsulfonic acid, allylphosphonic acid and methallylsulfonic acid.
• the proportion by weight of comonomers of component B), based on the The total mass of the polymers can be 0 to 99.8% by weight preferably 0.5 to 80% by weight, particularly preferably 2 to 50% by weight.
• the substances are Component BC) selected from the comonomers of component C).
• Comonomers of component C) are all olefinically unsaturated Monomers with cationic charge in question that are capable of being selected in the Reaction media with acryloyldimethyltauric acid or its salts copolymers form.
• the resulting distribution of the cationic charges over the chains away can be statistical, alternating, block-like or gradient-like.
• cationic comonomers of component C) are also to be understood as those the cationic charge in the form of a betainic, zwitterionic, or wear amphoteric structure.
• the comonomers are the Component C) from olefinically unsaturated, cationic comonomers which have at least one oxygen, nitrogen, sulfur or phosphorus atom and have a molecular weight less than 500 g / mol.
• Comonomers of component C) are also within the meaning of the invention aminofunctionalized precursors, which by polymer-analogous reactions in their corresponding quaternary (e.g. reaction with dimethyl sulfate, methyl chloride), zwitterionic (e.g. reaction with hydrogen peroxide), betaine (e.g. reaction with chloroacetic acid), or amphoteric derivatives can be transferred.
• DMAC Diallyldimethylammonium chloride
• MATAC [2- (methacryloyloxy) ethyl] trimethylammonium chloride
• AMTAC [2- (acryloyloxy) ethyl] trimethylammonium chloride
• MEAAC [2-methacrylamidoethyl] trimethyl ammonium chloride
• MEAmido [2- (acrylamido) ethyl] trimethylammonium chloride
• N-methyl-4-vinyl pyridinium chloride dimethylaminoethyl dimethylaminopropylmethacrylamide
• Methacryloylethyl-N-oxide Methacryloylethyl-N-oxide and / or Methacryloylethyl betaine.
• the proportion by weight of comonomers of component C) can, based on the Total mass of the polymers, 0.1 to 99.8% by weight, preferably 0.5 to 30% by weight and particularly preferably 1 to 20 wt .-%.
• the inventive Crosslinked polymers i.e. they contain comonomers with at least two polymerizable vinyl groups.
• Preferred crosslinkers are methylene bisacrylamide; methylenebismethacrylamide; ester unsaturated mono- and polycarboxylic acids with polyols, preferably diacrylates and Triacrylates or methacrylates, particularly preferably butanediol and Ethylene glycol diacrylate or methacrylate, trimethylolpropane triacrylate (TMPTA) and Trimethylolpropane trimethacrylate (TMPTMA); Allyl compounds, preferred Allyl (meth) acrylate, triallyl cyanurate, maleic acid diallyl ester, polyallyl ester, Tetraallyloxyethane, triallylamine, tetraallylethylene diamine; Allylester the Phosphoric acid; and / or vinylphosphonic acid derivatives.
• polyols preferably diacrylates and Triacrylates or methacrylates, particularly preferably butanediol and Ethylene glycol diacrylate or methacrylate, trimethylolprop
• TMPTA Trimethylolpropane triacrylate
• the proportion by weight of crosslinking comonomers, based on the total mass of the polymers, is preferably up to 20% by weight, particularly preferably 0.05 to 10% by weight and particularly preferably 0.1 to 7% by weight.
• Preferred polymers are those obtained by copolymerization of substances at least components A), C) and D) are available.
• polymers are those which are obtained by copolymerization of Substances of at least components A), C) and E) are available.
• polymers are those which are obtained by copolymerization of Substances of at least components A), D) and F) are available.
• polymers are those which are obtained by copolymerization of Substances of at least components A) and F) are available.
• Solvents are used that relate to radical polymerization reactions behave largely inert and advantageously the formation of medium or high Allow molecular weights.
• Water is preferred; lower alcohols; preferably methanol, ethanol, propanols, iso-, sec.- and t-butanol, particularly preferably t-butanol; Hydrocarbons from 1 to 30 Carbon atoms and mixtures of the aforementioned compounds.
• the polymerization reaction is preferably carried out in the temperature range between 0 and 150 ° C, particularly preferably between 10 and 100 ° C, both at normal pressure and even under increased or reduced pressure. If necessary, the Polymerization also under a protective gas atmosphere, preferably under Nitrogen.
• High-energy electromagnetic radiation, mechanical energy or the usual chemical polymerization initiators such as organic peroxides, for example benzoyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, cumene hydroperoxide, dilauroyl peroxide or azo initiators, such as, for example, azodiisobutyronitrile (AIBN), can be used to trigger the polymerization.
• organic peroxides for example benzoyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, cumene hydroperoxide, dilauroyl peroxide or azo initiators, such as, for example, azodiisobutyronitrile (AIBN)
• AIBN azodiisobutyronitrile
• inorganic peroxy compounds such as (NH 4 ) 2 S 2 O 8 , K 2 S 2 O 8 or H 2 O 2 , optionally
• an aliphatic or aromatic sulfonic acid for example benzenesulfonic acid, toluenesulfonic acid etc.
• All solvents which relate to one another can serve as the polymerization medium radical polymerization reactions behave largely inert and the Allow formation of high molecular weights.
• Preferred. Use water and lower, tertiary alcohols or hydrocarbons with 3 to 30 carbon atoms.
• t-butanol as the reaction medium used.
• Mixtures of two or more representatives of the described potential solvents are of course also in accordance with the invention.
• This also includes emulsions of immiscible solvents (e.g. Water / hydrocarbons).
• all types of reaction management suitable suitable which lead to the polymer structures according to the invention (e.g. Solution polymerization, precipitation process, suspension process).
• Precipitation polymerization is particularly suitable, particularly preferably that Precipitation polymerization in tert-butanol.
• Copolymers No. 1 to No. 69 are 1 or according to the following production method 2 can be synthesized.
• This process is suitable for polymers which are used in precipitation processes in one organic medium (preferably t-butanol, aqueous t-butanol) can be produced.
• the monomers are initially introduced in the appropriate solvent, optionally neutralized and then by adding an initiator polymerized.
• the resulting polymer suspension is sufficient stirred for a long time.
• the subsequent stirring phase becomes the boiling point.
• the liquid becomes later Medium and all auxiliaries are added to the polymer suspension with stirring and then the lower-boiling former polymerization medium by distillation away.
• the Polymer suspension stirred as long as necessary, if necessary with the addition of heat and / or adding other ingredients (e.g. water, active substances, etc.) until the desired consistency and performance is achieved.
• This process is suitable for polymers which are used in solution processes in one organic medium (preferably t-butanol, aqueous t-butanol) can be produced.
• the monomers are initially introduced in the appropriate solvent, optionally neutralized and then by adding an initiator polymerized. To complete the reaction and minimize the Residual monomer concentration, the resulting polymer solution is long enough touched.
• the subsequent stirring phase in the Boiling heat carried out.
• the later liquid medium and all auxiliaries are added to the polymer solution with stirring and then the lower-boiling former polymerization medium is removed by distillation. to Completion of the separation and gentle processing can be done be worked in a vacuum.
• the polymer solution as long as stirred, optionally with the addition of heat and / or addition other ingredients (e.g. water, active substances, etc.) until the desired one Consistency and performance is achieved.
• the concentrates according to the invention contain an organic one Solvent or solvent mixture whose boiling point is at least 10 ° C is higher than that of the polymerization medium used, preferably oils from the Group of hydrocarbons, ester oils, vegetable oils and silicone oils.
• oils used according to the invention include hydrocarbon oils with linear or branched, saturated or unsaturated C 7 -C 40 carbon chains, for example petrolatum, dodecane, isododecane, cholesterol, lanolin, hydrogenated polyisobutylene, docosane, hexadecane, isohexadecane, paraffins and isoparaffins; Oils of vegetable origin, in particular liquid triglycerides such as sunflower, corn, soybean, rice, jojoba, babusscu, pumpkin, grape seed, sesame, walnut, apricot, macadamia, avocado, sweet almond, Cuckoo flower, castor oil, olive oil, peanut oil, rapeseed oil and coconut oil; Oils of animal origin, for example beef tallow, lard, goose fat, perhydrosqualene, lanolin; synthetic oils such as purcellin oil, isoparaffin, linear and / or branched fatty alcohols and fatty acid esters, preferably Gu
• Suitable silicone oils are dimethylpolysiloxanes, cyclomethicones, polydialkylsiloxanes R 3 SiO (R 2 SiO) x SiR 3 , where R is methyl or ethyl, particularly preferably methyl, and x is a number from 2 to 500, for example those under Trade names VICASIL (General Electric Company), DOW CORNING 200, DOW CORNING 225, DOW CORNING 200 (Dow Corning Corporation), available Dimethicone, Trimethylsiloxysilicate [(CH 2 ) 3 SiO) 1/2 ] ⁇ [SiO 2 ] y , where x represents a number from 1 to 500 and y represents a number from 1 to 500, dimethiconols R 3 SiO [R 2 SiO] x SiR 2 OH and HOR 2 SiO [R 2 SiO] x SiR 2 OH, where R is methyl or Ethyl and x stands for a number up to 500, polyalkyla
• the concentrates according to the invention can optionally contain emulsifiers and / or water contain.
• Suitable emulsifiers are adducts of 0 to 30 mol of alkylene oxide, in particular ethylene, propylene, butylene oxide, with linear fatty alcohols with 8 to 22 carbon atoms, with fatty acids with 12 to 22 carbon atoms, with alkylphenols with 8 to 15 carbon atoms.
• Atoms in the alkyl group and on sorbitan esters (C 12 -C 18 ) fatty acid monoesters of adducts of 0 to 30 moles of ethylene oxide with glycerol; Glycerol monoesters and diesters and sorbitan monoesters and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and optionally their ethylene oxide addition products; Addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil; Polyol and especially polyglycerol esters such as polyglycerol polyricin oleate and polyglycerol poly-12-hydroxystearate. Preferred are liquid fatty acid esters which can be both ethoxylated (PEG-10 polyglyceryl-2 laurate) and non-ethoxylated (polyglyceryl-2 sesquiisostearate).
• sorbitol esters prepared by reacting sorbitol with fatty acid methyl esters or Fatty acid triglycerides.
• the fatty acid residue in fatty acid methyl esters and Fatty acid triglycerides generally contain 8 to 22 carbon atoms and can be straight-chain or be branched, saturated or unsaturated. Examples include palmitic acid, Stearic acid, lauric acid, linoleic acid, linolenic acid, isostearic acid or oleic acid.
• oils and fats come as fatty acid triglycerides and waxes in question, for example olive oil, rapeseed oil, palm kernel oil, Sunflower oil, coconut oil, linseed oil, castor oil, soybean oil, possibly also in refined or hydrogenated form. Because these natural fats, oils and waxes usually mixtures of fatty acids with different chain lengths represent, this also applies to the fatty acid residues used in the invention Sorbitol esters.
• the sorbitol esters used according to the invention can also be alkoxylated, preferably ethoxylated.
• anionic emulsifiers such as ethoxylated and non-ethoxylated mono-, di- or tri-phosphoric acid esters, but also cationic emulsifiers such as mono-, di- and tri-alkyl quats and their polymeric derivatives are used.
• the concentrates according to the invention are suitable as thickeners, consistency enhancers, Emulsifier, solubilizer, dispersant, lubricant, adhesive, conditioner and / or Stabilizer - excellent for the formulation of cosmetic, pharmaceutical and dermatological agents, in particular in the form of oil-in-water emulsions of creams, lotions, cleansing milk, cream gels, spray emulsions, e.g. Body lotions, after-sun lotions, sunscreens and deodorant sprays.
• the invention therefore also relates to cosmetic, pharmaceutical and dermatological preparations containing a concentrate, which after the process according to the invention has been produced.
• the concentrates according to the invention are in the cosmetic and pharmaceutical preparations used in weight quantities that Polymer concentrations of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, particularly preferably 0.5 to 3% by weight, based on the finished agent, result.
• the agents according to the invention can be anionic, cationic, nonionic, zwitterionic and / or amphoteric surfactants, as well as further auxiliaries and additives, cationic polymers, film formers, superfatting agents, stabilizers, biogenic Active ingredients, glycerin, preservatives, pearlescent agents, colors and fragrances, Solvents, opacifiers, protein derivatives such as gelatin, Collagen hydrolyzates, polypeptides on a natural and synthetic basis, egg yolk, Lecithin, lanolin and lanolin derivatives, fatty alcohols, silicones, deodorants, Substances with keratolytic and keratoplastic effects, enzymes and Carrier substances included. Furthermore, the agents according to the invention antimicrobial agents are added.
• the agents according to the invention can be organic solvents contain.
• organic solvents polyhydric alcohols.
• Alcohols with 1 to 4 are preferred Carbon atoms such as ethanol, propanol, isopropanol, n-butanol, i-butanol, t-Butanol, glycerin and mixtures of the alcohols mentioned.
• Other preferred alcohols are polyethylene glycols with a relative Molecular mass below 2000. In particular, use of polyethylene glycol a molecular weight between 200 and 600 and in amounts up to 45 % By weight and of polyethylene glycol with a relative molecular mass between 400 and 600 in amounts of 5 to 25% by weight are preferred.
• solvents are triacetin (glycerol triacetate) and 1-methoxy-2-propanol.
• Short-chain anionic surfactants in particular aryl sulfonates, act hydrotropically, for example cumene or toluenesulfonate.
• Example A4 polymer concentrate with high emulsifier content
• the polymer concentrates A1 to A3 as well as A5 and A6 are processed in an analogous manner manufactured.
• Example B6 Polymer concentrate with low emulsifier content
• the polymer concentrates B1 to B5 are produced in an analogous manner
• Example C1 polymer concentrate without emulsifier
• reaction solution After completion of this phase (about 20-30 minutes) the reaction solution is heated to boiling temperature and boiled for 2 hours to complete the reaction.
• the reflux condenser is then replaced by a distillation bridge and the main amount of t-butanol is removed by distillation.
• 178 g of myrithil 318 (later corresponds to 64% by weight) are added to the polymer concentrate.
• the polymer completely dissolves in the solvent.
• the residues of the reaction butanol are removed from the mixture by applying a vacuum. Care must be taken that the vacuum applied enables the t-butanol to be removed by distillation, but the boiling point of the solvent, which corresponds to this pressure, is not exceeded.
• the mixture After the t-butanol has been separated off, the mixture is cooled and the product is discharged from the flask.
• the polymer concentrate C2 is produced in an analogous manner.
• Polymer concentrates were assessed for their appearance, viscosity and stability (sedimentation when stored at 25 ° C., 3 weeks).
• Polymer concentrates A1-A6, B1-B6, C1 and C2 1.
• High emulsifier concentration Polymer No. 18 22 17 41 22 22 A1 A2 A3 A4 A5 A6 polymer 36.0% 36.0% 36.0% 36.0% 36% Hostacerin DGI 25.6% 12.8% 51.2% 25.6% 28.8% 30% Hostaphat KL 340 D.
• C1, C2 transparent solutions
• pourable (viscosity ⁇ 10000 mPas) Chemical designation of the commercial products used: Hostacerin DGI Polyglyceryl-2 sesquiisostearate Myritol 318 Caprylic / Capric triglycerides IPP isopropyl palmitate Hostaphat KL340D Trilaureth-4 phosphate

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• 2003
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